Stabilization of fat products



Patented May 29, 1945 UNITED STATES PATIENT OFFICE 2,877,031 v STABILIZATION OF FAT PRODUCTS Frank A. Norris, Minneap are used together, however, they'exhibit a pronounced synergistic eilect which gives the product a stability far in excess of that of the untreated product. This is demonstrated by the following table showing the effect on rendered pork fat. 66

olis, Minn., minor to General Mills, Inc., a corporation oi Delaware No Drawing. Application June 19, 1944, Serial No. 541,116. In Canada September 2, 1943 14 Claims. (Cl. 99-163) The present invention relates to a process of Table! stabilizing fatty products against the development of rancidity, and to the resultant product. "Swift" The invention is directed particularly to fatty 58mph mi food products, such as oils, shortenings, salad dressings, spreads, and the like.

The present application is a continuation-in- ;Ii g 12: 6fii6ii'cl& 2 part of my co-pending application Serial No. 511,- g; g gj j: 33mg ggig g, 373, filed November 22, 1943, which in turn is a continuation-in-part of my application Serial No. l0 In place of hascorblc acid other compounds haw med 1943' ins the ene-diol grouping, such as reductone, di-

The present invention involves a synergistic hydroxymalem acid analogues r isomers of asantioxidant efiect resulting from the combined comic acid such ismascurbm acid g1ucas use of a plurality of substances. It has been comic ambbascorblc etc maybeused found that combinations of certain antioxidants It It also been a a that a multiple symb produce a resultant stability far in excess of the gist: efiect is obtained m addition to the Syner sum the abilities obta'med by the use of gistic effect mentioned above whenaheterocyclic the compounds singly oxygen compound of the ime shown below is em- It is therefore a primary object of the present ployed m addition to the p amm be-nz1c acid invention to provide a process of stabilizing fatty and a compound having the enednol group The or oleaginous materials against oxidation and the heterocycnc oxygen compounds which d be devempment of rancidlty' employed to produce this multiple synergy It is another object of the invention to provide fall within the following classes. (1) The 0mm "products containing fats or oils which are stabimans as for example the hydrxychmmans lized against oxidation and the development 01' a the smmroxchmmans' the alpha" beta rancldm" and gamma tocopherols, the alkyl tocols such as A further object of the invention is to provide the 5 mmmethyltmols. and the chmmama a process of stabilizing fatty or oleaginous prodqmmes. It i8 intended that we term .l fi uctsbymeansofantioxidants which exhibit synermans" 5mm include the ehmmamsfiflummesi gist: 91mm both herein and in the claims. 2) The chro- These and other objects of the invention will menes as for example, the hydroxychmmenes be apparent from. the following description of the Such as me fi hydroxychmmenes and more invention with particular reference to specific extjcumfly 6 hydmxy 2 2 4 trimethylcmongene amples winch are to be understood as illustrative The communes for example w Only and not as limiting the invention droxycoumarones suth as the b-hydroxycou- It has been found that a synergistic antioximamnes and more particularly 5 hydroxy 2467 dam effect obtained by the conjoint use of tetramethylcoumarone. (4) The coumarans as amino-benzoic acid and compounds containing for example the hydroxycoumamns, such as'the the ene'diolgmup 40 b-hydroiqcoumarans and more particularly 5- A hydroxy-2,4,6,7-tetramethylcoumaran, and the isoand hydroxyisocoumaranones such as the 5- such as l-ascorbic acid, vitamin C. While asand 7* y r0Xyisocoumaranones and more particcorbic acid, which is water-soluble, has been ularly B-D B Y I HE, -hYd yknown to have antioxidant effect in aqueous l y mn n and -hy Y- media, it has not been particularly eiiective in the phenylisocoumaranone. The terms coumarans fats probably because of its extremely low soluand y xy umarans are intended to include bility. Likewise, .p-amino-benzoic acid by itself the mr mone n the hy ro yl OcOuhas not demonstrated any appreciable antioxia an nes herein and in the claims. dant eilect in fats. When these two compounds These ompounds are all somewhat related to vitamin E and methods for their preparation can be found in the literature on the subject. Some of these compounds, particularly the tocopherols, occur naturally in vegetable oils and a suiiicient quantity may be present naturally in which case no addition from an external source would be necessary.

The synergistic action of these compounds is demonstrated by the following table showing the effectiveness of tocopherol, l-ascorbic acid and p amino-benzoic acid on renderedpork fat.

Table H Sample I p-amino-benzoic The tocopherol employed was a mixture of alpha, beta and gamma tocopherols with the gammo tocopherol predominating. It was employed in the form of a concentrate and the amount of concentrate employed was sufficient to give 0.02 per cent tocopherol, by weight, in the stabilized rendered pork fat. The rendered pork fat employed was the article available on the market, and it was used in these tests without any additional purification. Hydrogenation of this impure material results in a decided increase in stability. The material employed for these tests, however, was not hydrogenated in view of the fact that even without this treatment the time required for some of the tests was prolonged for weeks because of the high stabilities. It will be apparent, however, that the process may be employed on other materials having originally higher stabilities, in which case it may be desirable to reduce the amount of antioxidant added. I

Instead of the amounts of antioxidants shown above it is possible to employ decidedly lower concentration where such a high stability is not necessary. For example, it has been found that a rendered pork fat of about 6 hours initial stability was stabilized to a stability of about 43 hours by means of 0.0025 per cent tocopherol, 0.05 per cent p-amino-benzoic acid and 0.01 per cent l-ascorbic acid. The lower limit of antioxidant appears to be dictated by the resultant stability desired. There does not appear to be any upper limit to the amount of antioxidant which may be employed. However, the cost of the antioxidant constituents usually dictates that they should not be employed in much greater than 0.1 per cent.

It is desired to point out that an apparent discrepancy exists between sample 4 in Table I and sample '7 in Table II, both of which samples are composed of rendered pork fat of the same original stability to which 0.1 per cent p-aminobenzoic acid and 0.1 per cent l-ascorbic acid have been added. In the sample in Table I, th ingredients were merely weighed out and mixed together in an ordinary manner. In the sample in Table II the p-amino-benzoic acid and the l-ascorbic acid were thoroughly ground together in a mortar and the resultant mixture was ground with a small portion of rendered pork fat to effect an intimate suspension. It is believed that this intimate distribution of the antioxidant constituents is responsible for the increased stability found.

In addition to its effect on the antioxidant properties of the product, p-amino-benzoic acid has been found to have a decided preservative action and represses microbiological growth. The common materials employed to inhibit oxidative rancidity in fats have no eifect on microbiological growth. Consequently yeast, molds, and the like. continue to grow and producehydrolytic or other enzymic changes which result in rancidity. Thus, while the rancidity so produced is a distinct disadvantage in itself, the presence of large numbers of microorg is aneven greater disadvantage in view of the possible ill effect on those who consume such a product.

It is apparent that these various objectionsto the prior art are overcome by the present inven tion in that it inhibits both oxidative rancidity and microbiological growth; obviously hydrolytic and enzymic rancidity normally accom microbiological growth is likewise inhibited. These results are produced by means of substances which are recognized vitamins and which, therefore, perform additional functions when consumed. Therefore, there should be no objection to the use of these substances fiom the standpoint of the food and drug authorities, as each of these substances is found widely distributed in ordinary food products.

While particular reference has been made to the use of l-ascorbic acid as-the compound having the ene-dipl group in the multiple synergy, it is to be understood that other compounds having the ene-diol group, such as those specifically enumerated with respect to the single synergy, may also be used in the multiple synergy.

It is also to be understood that the invention is in no way limited to animal fats but may be employed on any product containing a substantial amount of, fat or oil, whether of animal or vegetable origin and whether edible or not, all of which products are contemplated by the term oleaginous material as used in the appended claims.

I claim as my invention:

1. A composition of matter comprising an oleaginous material containing, and being stabilized against the development of rancidity by, a compound containing an enediol group, p-aminobenzoic acid, and a compound selected from the group consisting of the chroman-5,6-quinones, hydroxychromans, the hydroxychromenes, the hydroxycoumarans, hydroxycoumarones.

2. A composition of matter comprising an oleaginous material containing, and being stabilized against the development of rancidity by, an ascorbic acid, p-amino-benzoic acid, and a compound selected from the group consisting of the chroman-5,6-quinones, hydroxychromans, the

hydroxychromenes, the hydroxycoumarans, and

the hydroxycoumarones.

3. A composition of matter comprising an ole-.

7 hydroxycoumarans, the hydroxycoumarones.

6. Process of stabilizing an oleaginous material which comprises incorporating therein an ascorbic acid, p-amino-benzoic acid, and a compound selected from the group consisting of the chroman-5,6-quinones, hydroxychromans, the hydroxychromenes, the hydroxycoumarans, the hydroxycoumarones.

'7. Process oi stabilizing an oleaginous material which comprises incorporating therein a compound containing an ene-diol group, p-aminobenzoic acid and a tocophercl.

8. Process of stabilizing an oleaginous material which comprises incorporating therein an ascorbic acid, p-amino-benzoic acid and a tocopherol.

9. An' edible shortening containing, and being stabilized against the development of rancidity by, a compound containing an ene-diol group, p-amino-benzoic acid, and a compound selected from the group consisting ofthe chroman-5,6- quinones, hydroxychromans, the hYGlOWChI'O- menes, the hydroxycoumarans, the hydroxycoumarones.

10. An edible shortening containing, and being stabilized against the development of rancidity by, an ascorbic acid, p-amino-benzoic acid and a tocopheroln 11. A composition of matter comprising an oleaginous material containing, and being stabilized against the development or rancidity by, not substantially in excess of .1 per cent or each of a compound containing an ene-diol group, pamino-benzoic acid, and a compound selected from the group consisting of the chroman-5,6- quinones, hydroxychromans, the hydroxychromenes, the hydroxycoumarans, the hydroxycou- 12. A composition of matter comprising an oleaginous material containing, and being stabilized against the development of rancidity by, not substantially in excess of .1 per cent of each of an ascorbic acid, p-amino-benzoic acid and a. tocopherol. y,

13. An edible shortening containing, and being stabilized against the development of rancidity by, not substantially in excess of .l per ,cent of each of a compound containing an ene-diol group, p-amino-benzoic acid, and a compound selected from the group consisting of the chroman-5,6-quinones, hydroxychromans, the hydroxychromenes, the hydroxycoumarans, the hydroxycoumarones.

14. An edible shortening containing, and being stabilized against the development of rancidity by, not substantially in excess of .1 per cent of each of an ascorbic acid, p-amino-benzoic acid and a tocopherol,

FRANK A. NORRIS. 

